Multifunctional superhydrophobic diatomaceous earth for chemical adhesion and color change

ABSTRACT

Provided herein is a multifunctional particle and methods of forming the same. The multifunctional particle includes: a silica particle; a hydrophobic silane; and a silane coupling agent; where each of the hydrophobic silane and the silane coupling agent are chemically bonded to the surface of the silica particle; where the multifunctional particle is superhydrophobic and chemically reactive.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. patent application Ser. No.14/357,552 filed on May 9, 2014, entitled MULTIFUNCTIONALSUPERHYDROPHOBIC DIATOMACEOUS EARTH FOR CHEMICAL ADHESION AND COLORCHANGE, the entire contents of which are incorporated herein byreference, and from which priority is claimed under 35 U.S.C. §120.Priority is also claimed under 35 U.S.C. §119 to International PatentApplication No. PCT/US2012/064581 filed on Nov. 11, 2012, the entirecontents of which are also incorporated herein by reference. Thisapplication also claims priority under 35 U.S.C. §119(e) to U.S.Provisional Patent Application No. 61/558,861 filed on Nov. 11, 2011,the entire contents of which are also incorporated herein by reference.

BACKGROUND

Diatomaceous earth nanoparticles (DE) may be functionalized withfluorocarbons or saturated hydrocarbons to become superhydrophobic, butare incapable of chemically bonding to anything due to the highlyunreactive self-assembled monolayer (SAM) of the fluorocarbons orsaturated hydrocarbons. Current coating technologies generallyincorporate fluorinated diatomaceous earth (FDE) into polymer solutions.The particles are held in by mechanical forces and can easily be rubbedout of the surface. The polymer surface typically is highly porous andvery rough.

BRIEF SUMMARY

In one embodiment, a multifunctional particle is provided. Themultifunctional particle comprising: a silica particle; a hydrophobicsilane; and a silane coupling agent; wherein each of the hydrophobicsilane and the silane coupling agent are chemically bonded to thesurface of the silica particle; wherein the multifunctional particle issuperhydrophobic and chemically reactive.

In a first aspect of the first embodiment, the silica particle comprisesa diatomaceous earth particle, a fused silica particle, or a rice huskash particle.

In a second aspect, alone or in combination with the first aspect of thefirst embodiment, the hydrophobic silane and the silane coupling agentare simultaneously bonded to the surface of the silica particle.

In a fourth aspect, alone or in combination with any of the previousaspects of the first embodiment, the hydrophobic silane bonds to thesurface of the silica particle before the silane coupling agent bonds tothe surface of the silica particle.

In a fifth aspect, alone or in combination with any of the previousaspects of the first embodiment, the silane coupling agent bonds to thesurface of the silica particle before the hydrophobic silane bonds tothe surface of the silica particle.

In a sixth aspect, alone or in combination with any of the previousaspects of the first embodiment, the silane coupling agent is selectedfrom the group consisting of amino-functional hydrocarbon silanes,N-(6-aminohexyl)-3-aminopropyltrimethoxysilane,aminohexylaminoethyltrimethoxysilane, aminopropyltrimethoxysilane,aminopropyltriethoxysilane,N-(2-Aminoethyl)-3-aminopropyl-trimethoxysilane,methyacryloxypropyl-trimethoxysilane, and combinations thereof.

In a seventh aspect, alone or in combination with any of the previousaspects of the first embodiment, the silane coupling agent comprisesamine silanes, olefin silanes, anhydride silanes, epoxy silanes, halogensilanes, hydroxyl silanes, dipodal silanes, acrylate silanes,sulfur-containing silanes, water based silanes, isocyanate silanes, orazide silanes.

In an eighth aspect, alone or in combination with any of the previousaspects of the first embodiment, the hydrophobic silane comprises amolecule of the structure:

Xy(CH3)(3-y)SiLR

where y is 1 to 3;

X is Cl, Br, I, H, HO, R′HN, R′2N, imidizolo, R′C(O)N(H), R′C(O)N(R″),R′O, F3CC(O)N(H), F3CC(O)N(CH3), or F3S(O)20, where R′ is a straight orbranched chain hydrocarbon of 1 to 4 carbons and R″ is methyl or ethyl;

L, a linking group, is CH2CH2, CH2CH2CH2, CH2CH2O, CH2CH2CH2O,CH2CH2C(O), CH2CH2CH2C(O), CH2CH2OCH2, CH2CH2CH2OCH2; and R is (CF2)nCF3or (CF(CF3)OCF2)nCF2CF3, where n is 0 to 24.

In a ninth aspect, alone or in combination with any of the previousaspects of the first embodiment, the hydrophobic silane comprises1H,1H,2H,2H-perfluorooctyltrichlorosilane.

In another embodiment, a method for producing a multifunctional particleis provided. The method comprising: providing a silica particle;contacting a hydrophobic silane to the surface of the silica particle tochemically bond the hydrophobic silane to the surface of the silicaparticle; contacting a silane coupling agent to the surface of thesilica particle to chemically bond the silane coupling agent to thesurface of the silica particle; wherein the multifunctional particle issuperhydrophobic and chemically reactive.

In a first aspect of the second embodiment, the silica particlecomprises a diatomaceous earth particle, a fused silica particle, or arice husk ash particle.

In a second aspect, alone or in combination with the first aspect of thesecond embodiment, the hydrophobic silane and the silane coupling agentare simultaneously bonded to the surface of the silica particle.

In a third aspect, alone or in combination with any of the previousaspects of the second embodiment, the hydrophobic silane bonds to thesurface of the silica particle before the silane coupling agent bonds tothe surface of the silica particle.

In a fourth aspect, alone or in combination with any of the previousaspects of the second embodiment, the silane coupling agent bonds to thesurface of the silica particle before the hydrophobic silane bonds tothe surface of the silica particle.

In a fifth aspect, alone or in combination with any of the previousaspects of the second embodiment, the silane coupling agent is selectedfrom the group consisting of amino-functional hydrocarbon silanes,N-(6-aminohexyl)-3-aminopropyltrimethoxysilane,aminohexylaminoethyltrimethoxysilane, aminopropyltrimethoxysilane,aminopropyltriethoxysilane,N-(2-Aminoethyl)-3-aminopropyl-trimethoxysilane,methyacryloxypropyl-trimethoxysilane, and combinations thereof.

In a sixth aspect, alone or in combination with any of the previousaspects of the second embodiment, the silane coupling agent comprisesamine silanes, olefin silanes, anhydride silanes, epoxy silanes, halogensilanes, hydroxyl silanes, dipodal silanes, acrylate silanes,sulfur-containing silanes, water based silanes, isocyanate silanes, orazide silanes.

In a seventh aspect, alone or in combination with any of the previousaspects of the second embodiment, the hydrophobic silane comprises amolecule of the structure:

Xy(CH3)(3-y)SiLR

where y is 1 to 3;

X is Cl, Br, I, H, HO, R′HN, R′2N, imidizolo, R′C(O)N(H), R′C(O)N(R″),R′O, F3CC(O)N(H), F3CC(O)N(CH3), or F3S(O)20, where R′ is a straight orbranched chain hydrocarbon of 1 to 4 carbons and R″ is methyl or ethyl;

L, a linking group, is CH2CH2, CH2CH2CH2, CH2CH2O, CH2CH2CH2O,CH2CH2C(O), CH2CH2CH2C(O), CH2CH2OCH2, CH2CH2CH2OCH2; and

R is (CF2)nCF3 or (CF(CF3)OCF2)nCF2CF3, where n is 0 to 24.

In an eighth aspect, alone or in combination with any of the previousaspects of the second embodiment, the method further includes rinsingthe silica particle with a solvent to remove impurities.

In a ninth aspect, alone or in combination with any of the previousaspects of the second embodiment, the method further includes rinsingthe silica particle with a solvent to expose SiOH groups on the silicaparticle; wherein the silane coupling agent reacts with at least oneSiOH group.

In a tenth aspect, alone or in combination with any of the previousaspects of the second embodiment, the multifunctional particle comprisesa self-assembled monolayer.

In still another embodiment, a multifunctional composition is provided.The composition comprising: multifunctional particles, wherein eachmultifunctional particle comprises: a silica particle; a hydrophobicsilane; and a silane coupling agent; wherein each of the hydrophobicsilane and the silane coupling agent are chemically bonded to thesurface of the silica particle;

wherein the multifunctional particle is superhydrophobic and chemicallyreactive.

In a first aspect of the third embodiment, the composition furtherincludes a binder solution for suspending the multifunctional particles.

In a second aspect, alone or in combination with the first aspect of thethird embodiment, the composition further includes a polymer selectedfrom the group consisting of thermosets, acrylates, methacrylates,polyesters, urethanes, epoxies, phenolics, thermoplastics, polydienes,polyvinyl chloride, polyphenylene sulfide, acrylics, maleic anhydride,vinyl acetate, diene-containing copolymers, halogen-modifiedhomopolymers, chlorosulfonyl-modified homopolymers, polyamides,polyesters, polycarbonates, polysulfones, olefins, and combinationsthereof.

In a third aspect, alone or in combination with any of the previousaspects of the third embodiment, the polymer is copolymerized with themultifunctional particles.

In a further embodiment, a method for forming superhydrophobic surfacesis provided. The method comprising: providing a plurality ofmultifunctional particles, each multifunctional particle comprising: asilica particle; a hydrophobic silane; and a silane coupling agent;wherein each of the hydrophobic silane and the silane coupling agent arechemically bonded to the surface of the silica particle; wherein themultifunctional particle is superhydrophobic and chemically reactive;and introducing the multifunctional particles to the surface of thesubstrate to form a superhydrophobic surface.

In a first aspect of the fourth embodiment, the introducing themultifunctional particles to the surface of a substrate to form asuperhydrophobic surface comprises: applying the multifunctionalparticles to the surface of the substrate.

In a second aspect, alone or in combination with the first aspect of thefourth embodiment, the method further comprises forming a suspension ofthe multifunctional particles in a binder solution.

In a third aspect, alone or in combination with any of the previousaspects of the fourth embodiment, the introducing the multifunctionalparticles to the surface of a substrate to form a superhydrophobicsurface comprises: mixing the multifunctional particles and a material.

In a fourth aspect, alone or in combination with any of the previousaspects of the fourth embodiment, the method further comprises formingthe substrate from the mixture.

In a fifth aspect, alone or in combination with any of the previousaspects of the fourth embodiment, the method further comprises applyingthe mixture to the substrate surface; and heating the substrate to curethe mixture.

In a sixth aspect, alone or in combination with any of the previousaspects of the fourth embodiment, the material comprises asphalt or apolymer, wherein the polymer comprises thermosets, acrylates,methacrylates, polyesters, urethanes, epoxies, phenolics,thermoplastics, polydienes, polyvinyl chloride, polyphenylene sulfide,acrylics, maleic anhydride, vinyl acetate, diene-containing copolymers,halogen-modified homopolymers, chlorosulfonyl-modified homopolymers,polyamides, polyesters, polycarbonates, polysulfones, olefins, orcombinations thereof.

In a seventh aspect, alone or in combination with any of the previousaspects of the fourth embodiment, the multifunctional particles arecovalently bonded to the substrate surface.

In an eighth aspect, alone or in combination with any of the previousaspects of the fourth embodiment, the substrate has insulatingproperties and corrosion resistant properties.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

The present embodiments are further described in the detaileddescription which follows in reference to the noted plurality ofdrawings by way of non-limiting examples of the present embodiments inwhich like reference numerals represent similar parts throughout theseveral views of the drawings and wherein:

FIG. 1 illustrates a multifunctional particle in accordance with variousembodiments of the disclosure;

FIG. 2 illustrates functionalized diatomaceous earth particles treatedwith ninhydrin in accordance with various embodiments;

FIG. 3 illustrates a scanned image of a Scanning Electron Microscopy(SEM) image of an epoxy coating with multifunctional particles inaccordance with various embodiments;

FIG. 4 illustrates a scanned image of a Scanning Electron Microscopy(SEM) image of an epoxy coating with fluorinated diatomaceous earthparticles in accordance with various embodiments;

FIG. 5 illustrates and image of a sample of wallboard having asuperhydrophobic epoxy coating applied thereto and a sample of wallboardhaving a polyvinyl chloride coating applied thereto in accordance withvarious embodiments;

FIG. 6 illustrates an image of a water drop contact angle forcharacterizing the hydrophobicity of a surface in accordance withvarious embodiments;

FIG. 7 illustrates an image of a water drop contact angle forcharacterizing the hydrophobicity of a surface in accordance withvarious embodiments;

FIG. 8 illustrates an image of a water drop contact angle forcharacterizing the hydrophobicity of a surface in accordance withvarious embodiments;

FIG. 9 illustrates an image of a water drop contact angle forcharacterizing the hydrophobicity of a surface in accordance withvarious embodiments;

FIG. 10 illustrates an image of a water drop contact angle forcharacterizing the hydrophobicity of a surface in accordance withvarious embodiments;

FIG. 11 illustrates an image of a water drop contact angle forcharacterizing the hydrophobicity of a surface in accordance withvarious embodiments;

FIG. 12 illustrates a SEM image of asphalt with diatomaceous earthparticles in accordance with various embodiments;

FIG. 13 illustrates a SEM image of an epoxy coating with diatomaceousearth particles in accordance with various embodiments; and

FIG. 14 illustrates a SEM image of unmodified asphalt in accordance withvarious embodiments.

DETAILED DESCRIPTION

The embodiments of the disclosure presented herein are directed tomultifunctional silica (SiO₂) particles that are superhydrophobic andchemically reactive. This multifunctional particle maintainssuperhydrophobicity but has surface groups available for chemicalreactivity. Silica particles can be surface treated to increasehydrophobicity and create superhydrophobic particles having a singlefunctionality. Bonding applications of such singly function particles,however, are purely mechanical since the hydrophobic treatment ischemically inert. In some embodiments, another silane can be used in asecondary treatment of the particle surface to attach a compound forchemical reactivity. This leads to the creation of a multifunctionalsuperhydrophobic nanoparticle which has the ability to chemically bondto a binding agent and retain superhydrophobic properties. This has beendemonstrated through reaction-based color change of multifunctionalparticles that maintain their superhydrophobicity. In furtherembodiments, the hydrophobic silane and silane coupling agent are bondedto the surface of the silica particle and form a continuous, functionalSAM (self-assembled monolayer) over the surface of the silica particle.

Multifunctional Particle

In some embodiments, the multifunctional particle comprises a silicaparticle, a hydrophobic silane chemically bonded to the surface of thesilica particle, and a silane coupling agent chemically bonded to thesurface of the of silica particle, where the multifunctional particle issuperhydrophobic and chemically reactive. Hydrophobic surfaces bind veryweakly with water, which makes drops of water form beads on the surface.A hydrophobic surface is generally defined and is defined herein as thatwhich has a contact angle greater than 90° with a drop of water. Asuper-hydrophobic surface is defined herein as that which has a contactangle greater than 150° with a drop of water at normal ambienttemperatures (about 25° C.). Further, for example, the multifunctionalparticle enhances adhesion of the silica particle to various materials.The multifunctional particle is capable of forming durable bonds, suchas covalent bonds, between organic and inorganic materials. Themultifunctional particle is further capable of reacting with a substrateand presenting the maximum number of sites with reactivity specific andaccessible to the matrix phase. Although the multifunctional particlesare described in terms of superhydrophobicity and chemical reactivity,it will be understood that any number of other properties orfunctionalities may also be attributable to the multifunctionalparticles. For example, other functionalities may include corrosionresistance, insulation, and the like.

The silica particle includes SiO₂ containing compounds. Exemplary silicaparticles include diatomaceous earth particles, fused silica, rice huskash particles, and the like. In some embodiments, the silica particlescomprise nanoparticles. Diatomaceous earth is a chalk-like, soft,friable, earthy, very fine-grained, siliceous sedimentary rock usuallylight in color, although white when pure. It is very finely porous andis very low in density, such that it floats on water until its surfaceis wetted, and is chemically inert to most liquids and gases. It alsodisplays low thermal conductivity and a high fusion point. Manysediments and sedimentary rocks are somewhat diatomaceous. The depositsresult from an accumulation in oceans or fresh waters of the amorphoussilica (opal, SiO₂nH₂O) cell walls of dead diatoms that are microscopicsingle-cell aquatic plants (algae). The fossilized skeletal remains—apair of symmetrical shells (frustules)—vary in size from less than 1micron to more than 1 millimeter but are typically 10 to 200 micronsacross. The frustules have a broad variety of delicate, lacy, perforatedshapes from discs and balls to ladders, feathers, and needles, whichprovide the partitioned surface of the DE that provides the surfacetopography conducive to the achievement of superhydrophobic propertiesof the embodiments disclosed herein when the surface is properly treatedin a manner that retains the surface topography but renders the surfacehydrophobic. The typical chemical composition of diatomaceous earth isabout 86% silica, 5% sodium, 3% magnesium and 2% iron.

DE is generally processed into two different products: natural-grade (oruncalcined) and calcined. The processing of natural-grade diatomiteconsists of crushing and drying. Crude diatomite commonly contains up to40 percent moisture and can include more that 60 percent water.Typically a primary crushing is carried out to the material as mined toyield a desired aggregate size. The crushed DE is subsequently milledand dried simultaneously where suspended particles of diatomite arecarried in a stream of hot gases. Flash and rotary dryers are used todry the material to a powder of approximately 15 percent moisture.Typical flash dryer operating temperatures range from 70 to 430° C.

The suspended particles exiting the dryer pass through a series of fans,cyclones, and separators. These sequential operations separate thepowder into various sizes, remove waste impurities, and expel theabsorbed water. These natural-milled diatomite products are then baggedor handled in bulk without additional processing. Natural-grade DE ispreferred for the practice of the invention.

For filtration uses, natural grade diatomite is calcined by heattreatment in gas- or fuel oil-fired rotary calciners, with or without afluxing agent. Straight calcining is used for adjusting the particlesize distribution for use as a medium flow rate filter aid. The productof straight calcining has a pink color from the oxidation of iron in theraw material, which is more intense with increasing iron oxide contentof the DE. Typical calciner operating temperatures range from 650 to1,200° C. For straight-calcined grades, the powder is heated in largerotary calciners to the point of incipient fusion, and thus, in thestrict technical sense, the process is one of sintering rather thancalcining.

DE treated in excess of 650° C. undergoes material and structuralchanges which is deleterious to the silicate surface functionality towhich the hydrophobic coating of the present invention is ultimatelybound and at slightly higher temperatures is deleterious to the highlypartitioned surface topography that enables superhydrophobic characterwhen coated with a hydrophobic material. The surface of uncalcined DE isthat of amorphous silica, more similar in composition to that ofprecipitated silica rather than pyrogenic silica. There is a reasonablyhigh silanol content to the DE surface that can be characterized ashaving strong hydrogen bonded silanols, moderate strength hydrogenbonded silanols and weak hydrogen bonded silanols. Upon warming nearlyall strongly hydrogen bonded silanols are lost when 650° C. is reached,moderate strength hydrogen bonded silanols are lost when 1,000° C. isachieved and above 1,000° C. the weak hydrogen bonded silanols are lost.For the practice of the invention it is desirable that although surfacebound water is reduced to a low level or completely removed, thepresence of at least some moderate strength hydrogen bonded silanols isintended to provide sufficient sites for bonding of the coating layerand thereby stabilizing the hydrophobic self-assembly monolayer coating.For this reason calcined DE is generally avoided for the practice of theinvention as most calcined DE has been treated in excess of 800° C. Thedesired surface topography formed by the diatoms and a sufficient amountof silanol functionality on the silicate surface to achieve thecontinuous SAM of the present invention is generally unavailable with DEthat is heat treated in excess of 800° C.

Exemplary hydrophobic silanes include a molecule of the structure:

X_(y)(CH₃)₍₃ _(_) _(3′))SiLR

where y is 1 to 3; X is Cl, Br, I, H, HO, R′HN, R′₂N, imidizolo,R′C(O)N(H), R′C(O)N(R″), R′O, F₃CC(O)N(H), F₃CC(O)N(CH₃), or F₃S(O)₂O,where R′ is a straight or branched chain hydrocarbon of 1 to 4 carbonsand R″ is methyl or ethyl; L, a linking group, is CH₂CH₂, CH₂CH₂CH₂,CH₂CH₂O, CH₂CH₂CH₂O, CH₂CH₂C(O), CH₂CH₂CH₂C(O), CH₂CH₂OCH₂,CH₂CH₂CH₂OCH₂; and R is (CF₂)nCF₃ or (CF(CF₃)OCF₂)nCF₂CF₃, where n is 0to 24. Exemplary hydrophobic silanes include fluoralkylsilanes (e.g.,1H, 1H, 2H, 2Hperfluorooctyltrimethoxysilane) and alkylsilanes (e.g.,octadecyltrichlorosilane).

Exemplary silane coupling agents include amine silanes, olefin silanes,anhydride silanes, epoxy silanes, halogen silanes, hydroxyl silanes,dipodal silanes, acrylate silanes, sulfur-containing silanes, waterbased silanes, isocyanate silanes, azide silanes, and/or combinationsthereof. Exemplary amine silanes include:n-(2-aminoethyl)-3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane,n,n′-bis[3-(triethoxysilyl)propyl]urea, ureidopropyltrimethoxysilane,3-aminopropylmethyldiethoxysilane,n,n′-bis[(3-trimethoxysilyl)propyl]ethylenediamine,n1-(3-trimethoxysilylpropyl)diethylenetriamine,m-aminophenyltrimethoxysilane,n-(3-triethoxysilylpropyl)-4,5-dihydroimidazole,n-methylaminopropyltrimethoxysilane,3-aminopropyltris(methoxyethoxyethoxy)silane,ureidopropyltriethoxysilane,n-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and/or combinationsthereof. Exemplary olefin silanes include:

styrylethyltrimethoxysilane, methacryloxypropyl-trimethoxysilane,vinyltriethoxysilane, triethoxysilyl modified poly-1,2-butadiene,vinylcthoxysiloxanc homopolymer, vinyltriacetoxysilane,vinylmethoxysiloxane homopolymer, allyltrimethoxysilane,vinyltriisopropoxysilane, and combinations thereof. Exemplary anhydridesilanes include (3-triethoxysilyl)propylsuccinic anhydride. Exemplaryepoxy silanes include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,(3-glycidoxy-propyl)trimethoxysilane, and combinations thereof.Exemplary halogen silanes include:

((chloromethyl)phenylethyl)trimethoxysilane,p-chloromethyl)phenyltrimethoxysilane, and combinations thereof.Exemplary hydroxyl silanes includen,n-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane. Exemplary dipodalsilanes include: bis(3-trimethoxy-silylpropyl)amine,tris(3-trimethoxysilyl propyl)isocyanurate,1,6-bis(trimethoxysilyl)hexane, vinylmethoxysiloxane homopolymer,trimethoxysilyl)propyl] ethylenediamine, trimethoxysilylpropyl modified(polyethylenimine), bis(trimethoxysilylethyl)benzene,1,8-bis(triethoxysilyl)octane, and combinations thereof. Exemplaryacrylate silanes include: (3-acryloxypropyl)trimethoxysilane,methacryloxypropyl-trimethoxysilane, and combinations thereof. Exemplaryisocyanate silanes includes 3-isocyanatopropyltriethoxysilane and thelike.

Exemplary sulfur silanes include: 3-mercaptopropyltrimethoxysilane,3-mercaptopropyl-methyldimethoxysilane,bis[3-(triethoxysilyl)propyl]tetrasulfide,3-methacryloxypropyl-bis(trimethylsiloxy)methylsilane, and combinationsthereof. Exemplary waterborne silanes include: aminopropylsilsesquioxanein aqueous solution,

aminoethylaminopropylsilsesquioxane in aqueous solution, and the like.Exemplary azide silanes include 6-azidosulfonylhexyl-triethoxysilane andthe like.

In some embodiments, the hydrophobic silane is chemically bonded to thesurface of the silica particle before the silane coupling agent ischemically bonded to the surface of the silica particle.

The hydrophobic silane, in some embodiments, is covalently bonded to thesurface of the silica particle. The surface functionalization of thesilica particle can be carried out with the neat hydrophobic silane, orthe precursor in a non-reactive solvent such as a hydrocarbon, an ether,or a fluorinated solvent. In some cases, the silica particle can havethe hydrophobic silane deposited on the silica particle surface from thevapor phase. The surface functionalization can be carried out with anadded non-nucicophilic proton acceptor such as a tertiary amine, forexample triethylamine or pyridine, to scavenge acidic byproducts of thereaction. A catalyst can be included to accelerate the formation of theSAM. Water can also be included in the formulation. The amount of addedwater will depend upon the amount of residual water on the pretreatedsilica particle and the nature of the hydrophobic silane used. Water canbe introduced as a liquid or a vapor. In many cases, water vapor fromambient air is sufficient to react with the hydrophobic silane tointerconnect the hydrophobic silane into the structured stable SAMcoating. The time and temperature needed for effective formation of theSAM coating will depend upon the structure of the hydrophobic silane andany solvent, scavenger, or catalyst used. With many of the hydrophobicsilanes the treatment can be carried out rapidly at normal roomtemperatures. In some embodiments, temperatures of about 0 to about 100°C. or more can be used. Reaction times can vary from as little as about2 minutes to about 24 hours depending on the hydrophobic silane andconditions used for the SAM formation. In general, any excesshydrophobic silane and by-products formed during deposition and bondingcan be readily removed from the surface by washing or in some cases byapplying a vacuum and/or heat.

The resulting silica particles, which are functionalized with thehydrophobic silane, can be dried before the silane coupling agent isbonded to the single silane functionalized silica particles. In someembodiments, the single silane functionalized silica particles arerinsed to remove impurities. For example, if a chlorine-containingsilane was used to functionalize the silica particles, then a rinsingprocedure can be used to remove the chlorine groups. This isaccomplished by taking single silane functionalized silica particles andrinsing it in hexane, then filtering and drying the particles to removeresidual chlorine groups on the surface. These clean particles are thenimmersed in hexane and mixed with the silane coupling agent and water.This allows for the silane coupling agent to bond to open Si—OH groupson the particle. These available bond sites are due to incompletefunctionalization of the particle due to steric effects or shortreaction times.

In other embodiments, the silane coupling agent is chemically bonded tothe surface of the silica particle before the hydrophobic silane ischemically bonded to the surface of the silica particle. The silanecoupling agent includes hydrolysable groups such as an alkoxy, acyloxy,halogen, or amine, which form reactive SiOH groups upon hydrolysis.Siloxane linkages are formed when the reactive SiOH groups of the silanecoupling agent condense with the SiOH groups on the surface of thesilica particles. The resulting silica particles, which arefunctionalized with the silane coupling agent, can be dried beforehydrophobic silane is bonded to the single silane functionalized silicaparticles.

In additional or alternative embodiments, the hydrophobic silane and thesilane coupling agent are simultaneously chemically bonded to thesurface of the silica particle. For example, hydrophobic silanes such asfluorosilanes that have a (m)ethoxy head group termination can be mixedwith similarly terminated silane coupling agents such that bothcompounds simultaneously bond to the particle. Methoxy and ethoxysilanes can be intermixed for reaction times, such that the methoxycompound will bond before the ethoxy compound. For example,6-aminohexyl-3-aminopropyltrimethoxysilane (coupling agent) and1H,1H,2H,2Hperfluorooctyltrimethoxysilane (hydrophobic silane) can besimultaneously mixed with water and hexane to deposit a multifunctionalSAM onto silica particles. In this way, trichlorosilanes, which producechlorine that reacts with the silane coupling agents, can be avoided. Insome embodiments, aminopropylsilanes are used to treat fluorinateddiatomaceous earth particles (FDE) to create fluoro-amino-diatomaceousearth.

In further embodiments, the multifunctional particle comprises apredetermined ratio of the hydrophobic silane and the silane couplingagent. The ratio of the silanes, in some embodiments, is based on theapplication of the multifunctional particles, the compositionformulation of the multifunctional particles, targeted properties, thetype of silane coupling agent, the type of hydrophobic silane, and thelike. The ratio of hydrophobic silane to silane coupling agent isdiscussed in further detail below.

Referring now to FIG. 1, an exemplary multifunctional nanoparticle withlong hydrocarbon chains for superhydrophobicity and amino-functionalchains for binding to polymers is illustrated. Not shown areinterlinking of silane head groups (—O—Si—O—Si—O—) on the nanoparticlesurface. The hydrocarbon chains are shown for simplicity but areinterchangeable for fluorocarbon chains.

To demonstrate that the multifunctional particles are chemicallyreactive, in some embodiments, a chemical indicator can be used tochange the color of the particles. These chemical groups of themultifunctional particle can also be tuned to certain colors by the useof adhesive pigments or by chemical reaction. Ninhydrin can be used forturning treated materials purple. For example, FIG. 2 showsmultifunctional particles 200 treated with ninhydrin that have turnedpurple as a result of the treatment. Non-multifunctionalsuperhydrophobic materials are colored by either fluorinating pigmentparticles or modifying the particle spacing or orientation in order totake advantage of surface optical properties to produce a color by lightrefraction and interference.

Compositions

Silica particles can be singly functionalized with one chemical to givehydrophobic surface functionality to the particle. Thisfunctionalization, combined with nanoscale surface roughness, leads to asuperhydrophobic material. Mechanical durability of such surfaces,however, is generally extremely low and thus unusable in real worldapplications as particles have no surface chemistry to bond to and aregenerally pinned to the surface mechanically. Polymers generallypolymerize around the particles and form voids surrounding them,allowing for mechanically pinning, but this also creates voids andfractures in the material due to the presence of non-polar particleswhich cannot meld with the polymer. This results in mechanical brushingor high energy water impacts that can easily remove the particles,allowing the surface to wet.

Addition of silane coupling agents to the nanoparticles allows forstrong covalent bonds to chemically bind the nanoparticle to a surfaceor allow for copolymerization of the particles into polymer chains.These coupling agents can be selected to specifically bind to any numberof materials in any given situation, allowing for customizablenanoparticles.

In some embodiments, a composition comprising the multifunctionalparticle is provided. In further embodiments, the composition furtherincludes a binder solution for dispersing the multifunctional particles,solvents, water, processing aids, fillers, color agents, biocides,polymers, asphalt, and/or other materials. Exemplary polymers includethermosets, acrylates, methacrylates, polyesters, urethanes, epoxies,phenolics, thermoplastics, polydienes, polyvinyl chloride, polyphenylenesulfide, acrylics, maleic anhydride, vinyl acetate, diene-containingcopolymers, halogen-modified homopolymers, chlorosulfonyl-modifiedhomopolymers, polyamides, polyesters, polycarbonates, polysulfones,olefins, and combinations thereof. In some embodiments, the polymers arecopolymerized with the multifunctional particles. For example, thepresence of a polymer-compatible SAM allows for multifunctionalparticles to copolymerize with pre-polymers, such as PVC, urethane,epoxies, and thermoresins, which will react with the reactive groups ofthe silane coupling agent. In other embodiments, the silane couplingagent is matched to the targeted polymer. For example, silane couplingagents with amine groups may be better suited to react or bind tofluorocarbons and styrene butadienes and less suited to bind to nitrileand isoprene. In some exemplary embodiments, the composition includesN-(2-Aminoethyl)-3-aminopropyltrimethoxysilane or another silanecoupling agent and epoxies, phenolics, melamines, nylons, PVC acrylics,urethanes, nitrile rubbers, thermoset polymers such as dialyphthalate,epoxy imide, melamine, paraffin, phenolic, polyester, urethane,cellulosics, polyacctal, polyamidc, polybutylene terephthalate, andpolycarbonates, as well as sealants such as polysulfides.

In some cases, when FADE (fluorocarbon/amino dual functionaldiatomaceous earth) is mixed with a pre-polymer, the resulting materialis vastly different than the same mixture having FDE (singly functionalfluorinated diatomaceous earth) instead of FADE. For example, mixing FDEand PVC (polyvinylchloride) cement results in a delicatesuperhydrophobic surface (e.g., not durable, easily broken), but mixingFADE with PVC cement results in a mechanically durable material that hasvery high hydrophobicity because the FADE particles have bonded directlyto polymer chains. Additionally, mixing FDE with a silicone thermoresinand heat treating results in a very rough and delicate superhydrophobicmaterial, while using FADE will result in a smooth and robust materialthat is very hydrophobic.

Additionally, particles can be treated in a “lock-key” fashion in whichone set of multifunctional particles can be treated with one side of anadhesive compound, and another set of multifunctional particles can betreated with the other side of the adhesive compound similar to atwo-part epoxy adhesive compounds. For example, an epoxy-type ofdiatomaceous earth package could be formulated in which particles A havean expoxidesilane (epoxy) and particles B can have amino-silane(hardener compound).

Combining these particles in such a fashion to facilitate a reactionthat results in the particles being crosslinked to one another, and thepresence of free fluorocarbon chains also gives the epoxysuperhydrophobicity. Exemplary silane coupling agents for use is theseepoxy systems include aminosilanes and acrylicsilanes. Mixtures of thesecompounds form a hard resin material upon heating, which results inparticles continuously embedded in a surface, having high mechanicaldurability to brushing or high energy water impacts.

Also provided herein are methods for forming superhydrophobic surfaces.In some embodiments, the multifunctional particles or a compositioncomprising the multifunctional particles are introduced to a surface ofa substrate. In some exemplary embodiments, the multifunctionalparticles are applied to the surface of the substrate. For example, acoating comprising the multifunctional particles may be sprayed,brushed, or rolled on the substrate surface, or the substrate may bedipped into the coating. In further embodiments, the multifunctionalparticles are covalently bonded to the surface of the substrate. Inother exemplary embodiments, the multifunctional particles may be mixedwith polymer or other material and a substrate may be formed from thepolymer. The multifunctional particles are dispersed in the substratesuch that the substrate has a superhydrophobic surface. The substratehaving a superhydrophobic surface may be formed from the mixture byextrusion, molds, heat curing, heating, air drying, and the like.

Examples Preparation of Compositions Comprising Singly Functional SilicaParticles

A) Polyvinylchloride (PVC) Cement Experiment

Combine in a Glass Beaker:

10.5 g methyl ethyl ketone (MEK)

1.0 g PVC cement

0.1 g 1H,1H,2H,2H-perfluorooctyltrichlorosilane (Rf—Si)

0.5 g FDE (fluorinated diatomaceous earth)

Blend the above mixture for at least 1 minute. Spray onto substrateusing a PREVAL® Spray Gun. The mixture results in a surface that issuperhydrophobic after drying, but that has low durability. Particlesare mechanically pinned to the coating and abrasion can dislodge them.Optionally, spray with a PDMS/Toluene mixture for an oleophobic coating.

B) Aramid Fiber Experiment

Combine:

50 g Acetone

5 g FDE

0.5 g FAS (Fluorocarbon Silane)

Blend the above mixture for 30 seconds, and then pour solution over eachside of KEVLAR® (aramid fiber) sample. Resulted in a superhydrophobicsurface, but the particles did not stick to the surface of the KEVLAR®sample.

Preparation of Multifunctional Particles:

A) Bonding Silane Coupling Agent Before Bonding Hydrophobic Silane

i) Formulation A

Combined in Glass Beaker

12.2 g DE

0.5 g APS (aminopropyltrimethoxysilane)

24.8 g EtOH (ethanol)

Blend the above mixture for 15 minutes. Add 34 g of EtOH to rinse thesides of the glass beaker. Pour EtOH out, leaving 64.6 g total solution.Dip borosilicate slide into the solution, leave immersed in the solutionfor 1 minute. Spray solution on mesh, plastic, and additionalborosilicate slide. Dry coated samples in direct sunlight. Some of thematerial stuck very well to the glass slide. Adhesion was judged bylight finger abrasion. The glass slides from the above experiment had ahard film that was scratch resistant. The solution that was poured intoa glass dish had dried out and formed a cake. These cakes were muchsturdier than the cakes that result from drying out fluorinated DE.

Mix for 1 minute:

0.6 g Rf—Si

68 g Xylol

Immerse coated glass slide for 1 minute in the above solution. Drysamples overnight in ambient conditions. Mix the remainingaminofunctional DE with Xylol/Rf—Si solution. Dip one glass slide insolution; leave in glass dish overnight. After drying, theamine-functional particles in the glass dish were found to besuperhydrophobic. Coated glass slide also showed hydrophobicity.

ii) Formulation B

Combine in a container and blend for several minutes:

100 g Hexane

7 g Diatomaceous Earth

1 g methacryloxypropyltrimethoxysilane

2 mL H2O

It was noted that the reaction was gaseous. The resulting functionalizedparticles were filtered off with coffee filters, and then rinsed bydecanting with hexane. The filtered particles were then heated at 15° F.to dry out the particles.

B) Bonding Hydrophobic Silane Before Bonding Silane Coupling Agent

i) Formulation A

Rinse Particles by Blending:

5.0 g FDE

37.1 g Hexane, then decant hexane.

Start with about 32 g of Clean FDE in Hexane:

Add 14.0 g Hexane

Add 1.0 g APTES RN-(2-aminoethyl)3-aminopropyltrimethoxysilane)]

Blend solution, allow to air dry.

The APTES to DE weight ratio was determined as follows:

The wetting surface (ws) of APTES=355 m2/g.

Assume the following DE surface area (milled): typical: 10-30 m2/g;DiaSource: 69.05 m2/g; Perma-Guard: 26-28 m2/g; milling estimate: 50-60m2/g.

Calculate the weight ratio to be 1/7th to 1/6th g APTES per g DE.

ii) Formulation B

Rising Step:

Combined in a container:

178.2 g FDE

Rinse 1: 217.5 g Hexane

Rinse 2: 242.6 g Hexane

Mix the FDE and the 217.5 g of hexane for 5 minutes with blender. Keepmixture container sealed and allow the FDE to settle. Decant the hexane,and then repeat the above step for Rinse 2. After two rinses, 174.3 g ofclean powder resulted.

Batch 1: Combine and blend after every addition:

30.0 g clean FDE (from the rinsing step above)

Add 46.5 g Hexane

Add 5 g (2-aminoethyl)-3-aminopropyltrimethoxysilane

Add 2 mL Distilled H2O

Add 19 g Hexane

After the 19 g of hexane is added, mix the Batch 1 for several minutes(solution is hot).

Batch 2: Combine and Blend after Every Addition:

30.0 g clean FDE (from the rinsing step above)

Add 75 g Hexane, plus an additional ˜20 g

Add 5 g AHS (aminohexylaminopropyltrimcthoxysilane)

Add 2 mL H2O

After the 2 mL of H2O is added, blend Batch 2 for 5 minutes (solution ishot). Heat both batches at 17° F. to remove hexane.

iii) Formulation C

Combine in a container and in order:

10 g FDE clean

66 g Hexane

1 g Acrylic silane methyacryloxypropyl-trimethoxysilane

14 g Hexane

1 mL H2O

Upon blending the above mixture, it was observed that initially therewere continuous plumes of hexane vapor and smell of a gas.

iv) Formulation D Combined in a container:

2.8 g FDE (cleaned)

18 g Hexane

0.6 g AHAPTMS (aminohexylaminopropyltrimethoxysilane)

0.5 g H2O

Stir the mixture by hand using a stirring instrument and decant theparticles. Recovered 4.8 g wet particles.

v) Formulation E

Combined in a container:

3.0 g FDE

19 g Hexane

0.6 g MAPTMS (methacryloxypropyltrimethoxysilane)

Stir the mixture by hand using a stirring instrument and decant theparticles. Recovered 3.8 g wet particles. When dried, 2.7 g grams orparticles was recovered.

Treating Multifunctional Particles with Ninhydrin:

To validate the chemical reactivity of the multifunctional particles,the particles were treated with an aminoalkylsilane, which is generallyused as a silane coupling agent. These nanoparticles were treated withninhydrin, a chemical indicator which shows the prescence of amino(—NH₂) groups by turning the surface blue or purple. Treating silicaparticles functionalized with only the hydrophobic si lanes resulted inyellow color, which is the same color as the ninhydrin.Fluorocarbon-functionalized diatomaceous earth was rinsed in hexane andfunctionalized with an aminoalkylsilane, and then these particles wererinsed to remove non-bound amino groups. Immersion of the nanoparticlesin a 0.5 wt % ninhydrin in isopropanol solution resulted in turning thesolution and nanoparticles deep purple. The purple color has remainedthrough many rinse/centrifuge/decant cycles with both hexane andisopropanol as the rinsing agent and through ultrasonication ofparticles to try and remove weakly bonded purple pigment groups from theparticle surface. The nanoparticles were dried and found to be stillsuperhydrophobic with the purple color change permanent, indicating thatthe nanoparticles can also have their color changed through chemicaltreatment. Mixing ninhydrin in FDE results in no change to the materialcolor. It has been found that FADE will change to lighter shades ofpurple depending on the age over the course of a week, suggesting thatthe amino groups react with air or humidity.

A) Procedure for Ninhydrin Treatment:

In a 2.0 mL microcentrifuge tube, put approximately 0.2 g ofmultifunctional particle powder into the tube (fill up to the 0.5 mLline). Fill the rest of the tube with ninhydrin solution. Close lid andshake tube to blend particles into the ninhydrin solution. Aminefunctional particles will show color change in the span of severalseconds through minutes to hours, depending on the concentration ofamine silanes on the particles.

B) Ninhydrin Treatment and Multifunctional Particle Preparation

Combine in a container:

50 g FDE (cleaned)

90 g Hexane

8.2 g AHS (aminohexylaminopropyltrimethoxysilane)

3 mL H2O Distilled

Plus additional 100 mL Hexane to get particles distributed into liquid.

Blend the FDE particles in the mixture for several minutes, and thenfilter the mixture with coffee filters. Heat the filtered mixture at230° F. to speed up hexane removal. Rinse the filtered multifunctionalparticles according to the rinse cycle procedure below two times priorto ninhydrin testing to help eliminate unbounded amino silanes from theparticles. After 24 hours, the multifunctional particles turned blue.

Rinse Cycle Procedure:

Place a small aliquot of particles in 2.0 mL microcentrifuge tube. Fillthe tube with fresh hexane.

Shake the tube to form a uniform solution. Centrifuge the solution at3300 RPM for 60 seconds.

Decant the solution and then refill the tube with fresh hexane andrepeat. After another decant, fill the tube with the ninhydrin solution.Particles changed color after reacting with ninhydrin.

After five days, the multifunctional particle powder was again treatedwith ninhydrin, but the powder turned a light purple and did not turn aspurple as the previously tested multifunctional particle powder despitebeing previously rinsed. To establish that the difference in the shadesof purple was not linked to hexane presence, the multifunctionalparticle powder was tested against a control. The control includedunfunctionalized DE powder that was rinsed 2 times with purified hexaneand tested with ninhydrin. No difference was seen between ahexane-rinsed diatomaceous earth and the control DE. It was concludedthat (—NH2) groups decay over time or react with air.

Preparation of Compositions that include Silica Particles andPolypropylene:

i) Control

Combine and blend:

4.1 g PP (polypropylene)

29 g Xylol

ii) Single Functional Particle Composition

Combine and blend:

5.0 g PP

1.2 g Phenyl-functionalized DE

39 g Xylol

Heat the control and the composition mixtures to 140° C., blend theheated mixture, and then pour the heated mixture into a mold. Thepolymer substrate was removed from the mold and found to lacksuperhydrophobicity.

iii) Methacrylate Silane Formulation:

15 g DE at room temperature

133 g Hexane

1.5 g Methacrylate silane

Plus <1 g H2O

iv) Octadecyltrichlorosilane Silane Formulation:

Rolled 3.0 g of PP in 1.0 g DE functionalized withoctadecyltrichlorosilane (ODCx). PP granules were covered with a thicklayer of ODCx. The coated granules were heated to 150° C. There was toomuch ODCx for the entire granule collection to melt together, but someof the granule collection conglomerated. This conglomeration wasobserved to be superhydrophobic and durable with moderate fingerrubbing.

v) Preparation of a Silica Particle/Polymer Construction

To prepare the construction, the interior surface of a mold ispre-dusted with a layer of appropriate particles and other necessarycatalysts/additives and the polymer melt is injected so that the powderbecomes stabilized on the surface of the resulting polymer part. Forexample, place a layer of functionalized diatomaceous earth onto adiamond like carbon (DLC) coated aluminum. Heat polymer (e.g., PP) andplace the polymer into a mold, then cover with another layer offunctionalized diatomaceous earth. Use another diamond-coated aluminumto press the coated PP mold into a sandwich construction.

Variation 1 (Paste Method):

Blend the functionalized diatomaceous earth into a solvent, making apaste, and then blend the paste into a hot polymer. In one experiment,0.3 g methacrylic functionalized diatomaceous earth was blended with 0.7g mineral spirits to make a paste, and then the past was blended withapproximately 12 g of heated PP.

Variation 2 (Blend Method).

Blend a multifunctional diatomaceous earth powder into a hot polymermelt. In these experiments, the polymer was placed into a mold andmelted at 40° F., and then removed from heat. Multifunctionaldiatomaceous earth was placed onto the surface of the polymer melt andmanually blended into the PP at roughly 3-10 wt %. An excess amount ofparticles was used, and unbounded particles were recovered for futureuse. The polymer blend was then placed back into the oven to heat at 400F for another 15-20 minutes.

Variation 3 (Press Method):

Press a multifunctional diatomaceous earth into the surface of a hotpolymer melt. In these experiments, the polymer was placed into a moldand melted at 400 F, and then removed from heat. The surface pressmethod is similar to the blend method, except the particles were brushedonto the surface at less than 1 wt % and lightly pressed for severalseconds. An excess amount of particles was used, and unbounded particleswere recovered for future use. The polymer blend was then placed backinto the oven to heat at 400 F for another 15-20 minutes.

vi) Test Observations for the Silica Particle/Polymer Construction

a) Fluorinated Silica Particles (single functionality): The constructionwas found to be not superhydrophobic because particles became concealedby the polymer during cure in the press and blend methods describedhereinabove. Some amount of superhydrophobicity was observed with thepress method, but these particles were not bound and simply washed awaywith water or were blown off with air.

b) Non-functionalized Silica Particles: The construction was observed tobe not superhydrophbic as particles became embedded into the material.

c) Amine-functionalized Silica Particles: The particles in thisconstruction were successful in maintaining surface coverage in theblend and press methods. These samples appeared to have the mostdurability to finger rubbing.

d) Vinyl-functionalized Silica Particles: The particles in thisconstruction were successful in maintaining surface coverage in theblend and press methods. These samples appeared to have the gooddurability to finger rubbing.

e) Azide-functionalized Silica Particles: The particles in thisconstruction had some success, although samples had some areas ofhydrophiliticity that could have been due to manufacturing technique.

f) Methacryloxy-, Octadecyl-, and Phenyl-functionalized SilicaParticles: These polymer blends were not superhydrophobic.

Although the constructions and compositions were prepared using PP, itwill be understood that any number of polymers can be used. It will befurther understood, that the polymer construction can also be preparedby processing the multifunctional silica particles as a polymer blendadditive such as in co-extrustion.

Preparation of Compositions that Include Silica Particles and Epoxies

Diatomaceous earth particles have a surface area of about 30 m²/g. Thesilanes used both have a coverage rating of about 300 m²/g. Thus, thetheoretical particle surface area is 150 m² and the silanes occupy 90m², for a total surface coverage of 60%. This is well in excess of whathas been shown to produce superhydrophobic DE, which is about 17%theoretical area when using chlorosilanes. By adding X amount ofaminosilane first, the aminosilanes will cover a certain percent of theparticle first, and then the 0.5 g of fluorosilane will completelysaturate the rest of the particle, then be rinsed out of the particlesin post-production. For example, putting 0.1 grams of silane on 5.0 g DEwould theoretically cover 20% of the particles, leaving 80% of thesurface for the fluorosilane. See Table 1 below for further details.

TABLE 1 Amount of Amine surface Fluorine surface Aminosilane X (g)coverage coverage 0 0 100%  0.1 20% 80% 0.2 40% 60% 0.3 60% 40% 0.4 80%20% 0.5 100%  0

Diatomaceous earth particles were functionalized according to theformulation provided below, having both fluorinated and alkylaminesilanes.

5.0 g DE

0.2 g FAOS (1H,1H,2H,2H-perfluorooctyltrimethoxysilane) (hydrophobicsilane)

0.1 g AHAPS (6-aminohexyl-3-aminopropyltrimethoxysilane) (couplingagent)

7 g Hexane

0.04 g Water

The resulting multifunctional particles constituted the FADE(fluorocarbon/amino multifunctional diatomaceous earth) particles. Anadditional lot of diatomaceous earth was functionalized with justfluorinated silanes. This constituted the FDE particles (a controlgroup).

These particles were used to create two powder coatings on aluminumcoupons as follows:

i) Base coat: Epoxy Powder

ii) Top coat: 80 wt % Epoxy Powder, 20% Diatomaceous earth powder

One coating incorporated FADE particles, the other used FDE particles.These powder coatings were deposited and cured according to manufacturerinstructions. First, the aluminum coupon was coated with the epoxypowder until the surface was saturated. The coupon was then coated withthe epoxy/diatomaceous earth powder blend until the surface wassaturated. The coupons were cured at 400° F. for 10 minutes, as per thepowder instructions.

After cooling, both coatings were mechanically dusted by hand and blownwith 30 psi of compressed air. The epoxy coating formulated with FADEparticles was superhydrophobic and the particles were not removed by thecompressed air. The top layer of the FDE coupon, on the other hand, didnot adhere to the coupon surface and was blown off, resulting in anon-superhydrophobic coating. Afterwards, the coupons were analyzed withSEM as shown in FIGS. 3 and 4. FIG. 3 illustrates an image of the theepoxy coating with the FADE particles and FIG. 4 illustrates an image ofthe epoxy coating with the FDE particles.

The presence of amino silanes on the FADE allowed chemical bonding ofthe diatomaceous earth to the epoxy chemicals, allowing chemical bondingof the particles to the surface as well as allowing epoxy polymers toform to the particle as opposed to concealing the particle. TheseFADE-Epoxy coatings are superhydrophobic and show increased levels ofmechanical durability over other non-multifunctionalized coatings asdetermined by abrasion resistance to an ungloved finger. This FADE-Epoxycoating showed to be resistant to high water pressure, which was unableto penetrate the coating and wet at all. Other coatings were found to besusceptible to the same high water pressure, creating areas where thesuperhydrophobic coating was wetted.

In the above FADE formulation, it is thought that the overall particlebehavior is dependent on the ratio of hydrophobic silane to(hydrophilic) silane coupling agent. That is, the particle has amajority of hydrophobic surface arca in order to produce asuperhydrophobic nanoparticle. The mass of hexane is based on largerscale production levels of hexane to diatomaceous earth ratios and wasnot found to be practical for this small scale testing.

Particles were coated as above, but the FADE were produced with varyingamounts of amino silane. These particles have a surface area of about 30m²/g, and the silanes used in this study have a surface coverage ratingof about 300 m2/g. Thus, 1.0 g of diatomaceous earth could be 100%covered by 0.1 g of total silane. However, the true amount of surfacecoverage is limited by steric hindrance and reaction time.

In order to facilitate the bonding of aminosilanes to the particle, theaminosilanes and water were blended into the solution first for severalminutes before addition of the fluorosilanes. Afterwards, 0.5 g offluorosilane was blended into the solution in order to maximizehydrophobic character of the rest of the particle. The amount of hexaneadded was largely irrelevant as long as it dissolved the particles. Allsamples had a small amount of water added to the solution (<0.1 g) tocatalyze the reaction (see Table 2 below).

TABLE 2 Control AM01 AM02 AM04 AM05 AM10 5.0 g DE 5.0 g DE 5.0 g DE 5.0g DE 5.0 g DE 5.0 g DE 0.0 g APS 0.1 g APS 0.2 g APS 0.4 g APS 0.5 g APS1.0 g APS 0.5 g FAOS 0.5 g FAOS 0.5 g FAOS 0.5 g FAOS 0.5 g FAOS 0.5 gFAOS 10 g Hex. 17 g Hex. 24 g Hex. 17 g Hex. 20 g Hex. 29 g Hex.

The particles were isolated and dried, then blended into epoxy powder atan 80 weight % epoxy powder to 20 weight % FADE ratio. Coatings weremade similar as discussed hereinabove with a pure bottom coat and an80/20 top coat sprayed onto drywall samples.

The control sample, with diatomaceous earth functionalized solely withthe FAOS and without the aminosilanc, was not superhydrophobic and hadno gloss. Visually, the samples with amine had increasing reflectanceand sheen with increasing amine content, similar to a control epoxypowder coat that had no diatomaceous earth. The contact angle ofsuperhydrophobic samples appeared to decrease with additional aminegroups to the particle. The samples also had increasing particleretention and durability with increasing amine content. The AM10 samplehad high gloss, but was not superhydrophobic, indicating amine levelshad overwhelmed the superhydrophobic properties of the particles.

Water contact angles were measured and are listed in Table 3 below. Dueto the angle of the samples, contact angles were measured and an averagewas used to characterize the 20 surface.

TABLE 3 WCA WCA Average Sample Left Right WCA Ctrl 00 142.177 118.072130.1245 AMO1 155.014 157.166 156.09 AMO2 152.583 152.033 152.308 AMO4151.849 151.821 151.835 AMOS 150.980 150.803 150.892 AM10 117.848116.259 117.0535

FIGS. 6-11 illustrate images of a water drop contact angle forcharacterizing the hydrophobicity of the epoxy coated surfaces. FIG. 6corresponds to the Ctrl 00 sample, FIG. 7 corresponds to the AMO1sample, FIG. 8 corresponds to the AMO2 sample, FIG. 9 corresponds to theAMO4 sample, FIG. 10 corresponds to the AMOS sample, and FIG. 11corresponds to the AM10 sample.

The mechanism of this transition between matte superhydrophobicity andglossy hydrophobicity is linked to the fact that particles withincreased amine content are able to have a higher concentration ofcovalent bonds to the polymer. The fluorinated particles will naturallynot link to the epoxy functional groups, resulting in a substrate thathas porous surface defects that interfere with optical reflectance.Adding aminosilane allows the epoxy to bond directly to the particle,and increasing the silane content results in more bonding sitesresulting in a uniform coating with increased reflectance properties andhigher glossiness. Higher covalent bonding content results in increasedmechanical durability, as the particles have more chemical links to thepolymer overall.

In some embodiments, the silane coupling agent used for chemical bondingmatches the targeted polymer to produce a coating with increaseddurability. For example, FADE AMO4 particles (1.0 g) were blended into aPVC cement (2.0 g) and MEK (10 g) solution, a typical superhydrophobiccoating formulation that has low durability. The resulting coating usingthe FADE was superhydrophobic but had very low durability, as particleswould easily be brushed off of the surface. To identify if the aminesites were reacted, ninhydrin indicator solution was applied to this PVCcoating as well as to the previous AMO4 sample. Ninhydrin will turnpurple in the presence of —NH and —NH2 groups.

The ninhydrin solution was absorbed by both coatings. As shown in FIG.5, the ninhydrin did not produce a purple reaction with the aminoparticles in the epoxy coating in the ninhydrin treated area 510 of theAMO4 coated sample 502, likely due to these particles having fullyreacted with the epoxy resin. The black streaks shown in FIG. 5 at theninhydrin treated area 510 resulted from isopropyl alcohol in theninhydrin solution streaking the black Sharpie marker used to designatedthe area 510. The ninhydrin did produce a purple reaction with thefunctionalized diatomaceous earth (AM04) in the PVC cement coateddrywall sample 520 as evidenced by the purples spots 530 (see FIG. 5).In this case, the PVC cement apparently did not react to theseparticular aminosilanes, resulting in a coating that has diatomaceousearth particles that are bound mechanically only in a low durabilitycoating. It is also evident that the chemical reaction did not influencethe superhydrophobicity of the coating.

Existing superhydrophobic diatomaceous earth technology does not usemultifunctionalized particles. This limits the applicable polymers forthese particles. For example, the base fluorinated particles cannotproduce a superhydrophobic coating when used with epoxy powder coatmaterials. When the diatomaceous earth has both amine functional silanesand fluorinated silanes, it is possible to produce a superhydrophobicepoxy powder coat material.

The above test results further show that altering the amount of aminesilane on the silica particle will influence the characteristics of theresulting coating. Increasing amine content will increase durability,glossiness, and particle retention while remaining superhydrophobic.Overloading the particle with aminosilane results in a coating thatresembles the base epoxy coating, in that it is very glossy yet is notsuperhydrophobic.

Preparation of Compositions that Include Silica Particles andAcrylonitrile Butadiene Styrene:

Combine and blend:

25.7 g MEK

1.8 g ABS (acrylonitrile butadiene styrene) Black

1.9 g FADE

Blend the above mixture with a magnetic stir bar. Hand dip a glass slideinto the mixture and bake the coated glass slide for several minutes at200° F. In the thin areas of the coating, the coating surface was notsuperhydrophobic, but the coating was superhydrophobic in thicker areas.Increase thickness by immersing the glass slide for about 20 seconds andthen bake the coated glass slide for 2 minutes at 200° F. The coatingwas observed to be durable as only a small amount of powder could berubbed off of the glass surface. The surface was also superhydrophobicafter being rubbed with a gloved hand to visibly remove powder from thesurface. A high pressure jet of water eventually applied to the coatedglass surface eventually wetted the surface.

Modification of the Above Formula:

Add 2 g ABS to remaining 26 g of solution, and repeat the above process.A thick and opaque coating that was applied to the glass was found to bedurable and superhydrophobic with no visible powder removed upon wiping.High pressure water wets surface and water rubbed on surface wets aswell, however, drying the surface restores the durable andsuperhydrophobic properties. Glass sample holds up to rubbing with anungloved finger and maintains near superhydrophobic roll off of 5-10degrees.

Preparations of Asphalt Compositions that Include Silica Particles:

A series of experiments were performed to modify low viscosity asphaltpaint, using either an organic solvent-based asphalt of water-basedasphalt. FIG. 12 illustrates a SEM image of asphalt coating withun-functionalized DE. The circular objects, for example the circularobject 1202, represent the particles of DE. As shown in the illustratedembodiment, the coating surface is very porous with many structurehaving high aspect ratios. FIG. 13 shows a SEM image of an epoxy-basedpolymer coating with multifunctional DE having a continuous surface,which is flat, non-porous, and that has good abrasive durability.Circular objects 1310 of FIG. 13 are DE particles. FIG. 14 shows an SEMimage of un-modified asphalt.

Method:

Diatomaceous earth functionalized with various fluorinated silanesand/or silane coupling agents (e.g., amine, methacryloxy, OTS) aredispersed in a toluene solution and blended into the asphalt paint. Theresulting solution is sprayed with a compressed air system onto surfacesfor evaluation. When diatomaceous earth is blended directly into asphaltpaint, it acts as a thixotropic agent and the resulting spray coating isgenerally not superhydrophobic. The coating can become superhydrophobicwhen the solution is diluted with toluene after particles have beenadded, but this is inconsistent. Most consistent results are blending ina toluene-DE paste into the asphalt.

1. Dilute 2.5 g multifunctional diatomaceous earth particles in 5.0 gtoluene

2. Blend the particles and toluene mixture into 2.5 g solvent-basedasphalt in air condition.

a) Add catalysts or additives while blending

b) If necessary, heat solution within a distillation column

3. Spray the mixture onto the surface of a substrate in several thincoats. Avoid ‘puddling’ the solution or otherwise creating wet gels inthe coating. Final coating thickness is about 2 mils after air drying.

4. Resulting coating is brown and superhydrophobic.

5. Different silanes, catalysts, and additives have shown to haveinfluence on final coating properties, such as ability to wet over time,abrasive durability, and water pressure resistance.

6. Particle Functionalization: Particles were loaded at a 1:10 weightratio of total silane to bulk powder silica particles in hexane with asmall amount of water added to the solution. Silanes were generallyassumed to have at least 300 m2/g of coverage, and the DE particlesgenerally have 30 m2/g of surface area. Particles with two silanes wereloaded at 60/40 or 70/30 weight percent ratios of hydrophobic silane(fluorocarbon) to silane coupling agent.

Test Results

a) Methacryloxy-functional silane coupling agents for multifunctionalparticles: these asphalt coatings had the best overall properties whenused with no other additives. The coatings were superhydrophobic and hadhigh durability and high water pressure resistance. Benzoyl peroxide wasused as a catalyst to increase bonding of methacryloxy particles toproduce more robust coating samples with the same magnitude ofdurability.

b) Octadecyl and phenyl functional silanes for multifunctionalparticles: resulted in coating with lower abrasive durability whencompared to the asphalt coating with methacryloxy silanes. Octoadecylbased coating had high durability and water pressure resistance. Phenylbased coating had mediocre durability.

c) Amine-functional silane coupling agents for multifunctionalparticles: adding ABS (acrylonitrile butadiene styrene) polymer to theasphalt and using amine silane coupling agents to functionalize the DEgenerated better test results than methacryloxy asphalts. Amine basedcoatings had low to mediocre durability with no additives, but thecoating had the highest durability of all additives once combined withABS.

d) Puddling the asphalt spray results in a black or otherwise very darkcoating that is smooth but not superhydrophobic.

e) Plain diatomaceous earth: asphalt becomes superhydrophobic, but haslow durability, low water pressure resistance, and wets over time.

f) Fluorocarbon singly functional DE: The asphalt coating issuperhydrophobic, but water droplets wet within seconds of sustainedcontact. Low durability and water pressure resistance. Further,fluorinated powder has decreased miscibility with hydrocarbon solvents.

Particles can be more easily blended with toluene when treated withchemically active silanes as well as fluorosilanes. Still further,fluorocarbon is not necessary to produce a superhydrophobic coating.

-   -   g) Additives:    -   1) Acryl Butadiene Styrene—Increased durability of methacryloxy        and amine asphalt blends. Made amine based coatings the most        durable asphalt coating.    -   2) Benzoyl Peroxide—Used with methacryloxy particles.

Applications

The multifunctional diatomaceous earth particles can be used to create amechanically robust superhydrophobic surface when combined with polymerbinders. This is due to copolymerization of the adhesive chains withmonomers, resulting in particles that are mechanically and chemicallybound to a given surface. For example, this superhydrophobic compositioncan be applied as a sealant on surfaces that are prone to waterpermeability and corrosion such as underground PVC pipes, wall board,underground building materials, pipe interiors, and power lineprotective sheaths. The composition can be applied as a biofouling pronematerial such as underwater pier structures. The composition can beapplied to enhance water flow on surfaces such as pipe interiors, boathulls, surf boards, other general water and snow sports products,gutters, under-deck draining structures, marine and aviation bilgeareas, and consumer product bottles.

The composition can be applied to concrete, asphalt roadways/racetracks,composite decking and wooden walking surfaces to prevent the absorptionof water, prevent the formation of ice, and decrease the drying time onthese surfaces. The composition could be applied to Radar radomes toprevent the absorption of water and prevent the formation of ice. Thecomposition can be applied to wood and paper products as a barrier toprevent surfaces from wetting and developing biological growths such asmold and mildew. The composition could be used in a mixture with wateror oil to allow for controlled compressibility of the mixture for use inshock absorbers, pressure sensors, and hydraulic systems. Thecomposition can be applied to heat pump condenser coils to reduce energyconsumption related to coil deicing. The composition can be applied tocircuit boards and other electronics to prevent electrical shorts due towetting. The composition can be applied to fiberglass and other thermalinsulating materials to prevent wetting and reduced functionality. Thecomposition can be applied to medical and personal hygiene devices toreduce the likelihood of water transferred bacteria and germs.

The silane coupling agents can be adjusted such that the multifunctionalparticles can chemically bond to natural and synthetic textiles, whichcan be used for swim suits, solvent-resistant clothing, and chemicalresistant military uniforms or other protective coating. Such textilescan be used as durable, robust, and scalable low-surface-energy textiletreatments for militarily relevant, synthetic textiles that will preventabsorption and adhesion of fine aerosols and that will shed most bulkliquids.

While the foregoing disclosure discusses illustrative embodiments, itshould be noted that various changes and modifications could be madeherein without departing from the scope of the described aspects and/orembodiments as defined by the appended claims. Furthermore, althoughelements of the described aspects and/or embodiments may be described orclaimed in the singular, the plural is contemplated unless limitation tothe singular is explicitly stated.

Additionally, all or a portion of any embodiment may be utilized withall or a portion of any other embodiment, unless stated otherwise.

While certain exemplary embodiments have been described and shown in theaccompanying drawings, it is to be understood that such embodiments aremerely illustrative of and not restrictive on the broad invention, andthat this invention not be limited to the specific constructions andarrangements shown and described, since various other changes,combinations, omissions, modifications and substitutions, in addition tothose set forth in the above paragraphs are possible. Those skilled inthe art will appreciate that various adaptations and modifications ofthe just described embodiments can be configured without departing fromthe scope and spirit of the invention. Therefore, it is to be understoodthat, within the scope of the appended claims, the invention may bepracticed other than as specifically described herein.

What is claimed is:
 1. A multifunctional particle comprising: a silicaparticle; a hydrophobic silane chemically bonded to at least a portionof the surface of the silica particle; a silane coupling agentchemically bonded to at least a portion of the surface of the silicaparticle; wherein, the silica particle is rinsed with a solvent aftercontacting at least one of the hydrophobic silane or the silane couplingagent to remove impurities and to remove any of the at least one of thehydrophobic silane or the silane coupling agent that are unattached tothe silica particle; and wherein the multifunctional particle issuperhydrophobic and chemically reactive.
 2. The particle of claim 1,wherein the silica particle comprises a diatomaceous earth particle, afused silica particle, or a rice husk ash particle.
 3. The particle ofclaim 1, wherein the ratio of the hydrophobic silane and the silanecoupling agent chemically reacted with the surface of the silicaparticle is from 5:1 to 3:1.
 4. The particle of claim 1, wherein thesilane coupling agent is selected from the group consisting ofamino-functional hydrocarbon silanes,N-(6-aminohexyl)-3-aminopropyltrimethoxysilane,aminohexylaminoethyltrimethoxysilane, aminopropyltrimethoxysilane,aminopropyltriethoxysilane,N-(2-Aminoethyl)-3-aminopropyl-trimethoxysilane,methyacryloxypropyl-trimethoxysilane, and combinations thereof.
 5. Theparticle of claim 1, wherein the silane coupling agent comprises aminesilanes, olefin silanes, anhydride silanes, epoxy silanes, halogensilanes, hydroxyl silanes, dipodal silanes, acrylate silanes,sulfur-containing silanes, isocyanate silanes, or azide silanes.
 6. Theparticle of claim 1, wherein the hydrophobic silane comprises a moleculeof the structure:X_(y)(CH3)_((3-y))SiLR where y is 1 to 3; X is Cl, Br, I, H, HO, R′HN,R′2N, imidizolo, R′C(O)N(H), R′C(O)N(R″), R′O, F₃CC(O)N(H),F₃CC(O)N(CH₃), or F₃S(O)₂O, where R′ is a straight or branched chainhydrocarbon of 1 to 4 carbons and R″ is methyl or ethyl; L, a linkinggroup, is CH₂CH₂, CH₂CH₂CH₂, CH₂CH₂O, CH₂CH₂CH₂O, CH₂CH₂C(O),CH₂CH₂CH₂C(O), CH₂CH₂OCH₂, CH₂CH₂CH₂OCH₂; and R is (CF₂)nCF₃ or(CF(CF₃)OCF₂)nCF₂CF₃, where n is 0 to
 24. 7. The particle of claim 1,wherein the hydrophobic silane comprises1H,1H,2H,2H-perfluorooctyltrichlorosilane.
 8. A multifunctionalcomposition, the composition comprising: multifunctional particles,wherein each multifunctional particle comprises: a silica particle; ahydrophobic silane chemically bonded to at least a portion of thesurface of the silica particle; a silane coupling agent chemicallybonded to at least a portion of the surface of the silica particle;wherein, the silica particle is rinsed with a solvent after contactingat least one of the hydrophobic silane or the silane coupling agent toremove impurities and to remove any of the at least one of thehydrophobic silane or the silane coupling agent that are unattached tothe silica particle; and wherein the multifunctional particle issuperhydrophobic and chemically reactive.
 9. The composition of claim 8,further comprising: a binder solution for suspending the multifunctionalparticles.
 10. The composition of claim 8, further comprising: a polymerselected from the group consisting of thermosets, acrylates,methacrylates, polyesters, urethanes, epoxies, phenolics,thermoplastics, polydienes, polyvinyl chloride, polyphenylene sulfide,acrylics, maleic anhydride, vinyl acetate, diene-containing copolymers,halogen-modified homopolymers, chlorosulfonyl-modified homopolymers,polyamides, polyesters, polycarbonates, polysulfones, olefins, andcombinations thereof.
 11. The composition of claim 8, wherein thepolymer is copolymerized with the multifunctional particles.
 12. Amethod for forming superhydrophobic surfaces, the method comprising:providing a plurality of multifunctional particles, each multifunctionalparticle comprising: a silica particle; a hydrophobic silane chemicallybonded to at least a portion of the surface of the silica particle; anda silane coupling agent chemically bonded to at least a portion of thesurface of the silica particle; wherein, the silica particle is rinsedwith a solvent after contacting at least one of the hydrophobic silaneor the silane coupling agent to remove impurities and to remove any ofthe at least one of the hydrophobic silane or the silane coupling agentthat are unattached to the silica particle; and wherein themultifunctional particle is superhydrophobic and chemically reactive;and introducing the multifunctional particles to the surface of thesubstrate to form a superhydrophobic surface.
 13. The method of claim12, wherein the introducing the multifunctional particles to the surfaceof a substrate to form a superhydrophobic surface comprises: applyingthe multifunctional particles to the surface of the substrate.
 14. Themethod of claim 12, further comprising: forming a suspension of themultifunctional particles in a binder solution.
 15. The method of claim12, wherein the introducing the multifunctional particles to the surfaceof a substrate to form a superhydrophobic surface comprises: mixing themultifunctional particles and a material.
 16. The method of claim 12,further comprising: forming the substrate from the mixture.
 17. Themethod of claim 12, further comprising: applying the mixture to thesubstrate surface; heating the substrate to cure the mixture.
 18. Themethod of claim 15, wherein the material comprises asphalt or a polymer,wherein the polymer comprises thermosets, acrylates, methacrylates,polyesters, urethanes, epoxies, phenolics, thermoplastics, polydienes,polyvinyl chloride, polyphenylene sulfide, acrylics, maleic anhydride,vinyl acetate, diene-containing copolymers, halogen-modifiedhomopolymers, chlorosulfonyl-modified homopolymers, polyamides,polyesters, polycarbonates, polysulfones, olefins, or combinationsthereof.
 19. The method of claim 12, wherein the multifunctionalparticles are covalently bonded to the substrate surface.
 20. The methodof claim 12, wherein the substrate has insulating properties andcorrosion resistant properties.